Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
  • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
  • C07D498/10—Spiro-condensed systems
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/685—Compositions containing spiro-condensed pyran compounds or derivatives thereof, as photosensitive substances

Definitions

• the present invention relates to photochromatic compounds.
• the present invention relates to photochromatic compounds belonging to the group of spiro-isoindolino-oxazines, a process for their preparation and their use in polymeric materials.
• a further object of the present invention relates to polymeric compositions containing said photochromatic compounds and the photochromatic articles obtained from their processing.
• Photochromatic compounds are substances which have the characteristic of reversibly changing colour and/or degree of light transmission when exposed to solar or artificial light in the band ranging from UV to visible, or to some types of electromagnetic radiation, returning to their original state of colour and transmission when the initial light source is removed.
• organic photochromatic compounds those belonging to the groups of spiro-indolino-oxazines, spiro-pyranes and chromenes, are particularly known and used.
• the above compounds are capable of giving photochromatic characteristics to polymerized organic materials used, for example, in the production of photochromatic lenses for eye-glasses, special inks, toys, and in many other applications.
• the Applicant has now found photochromatic compounds belonging to the group of spiro-isoindolino-oxazines which have excellent photochromatic characteristics, excellent stress resistance and high dyability characteristics.
• the present invention therefore relates to photochromatic compounds belonging to the group of spiro-isoindolino-oxazines having general formula (I):
• R represents a linear or branched C 1 -C 10 alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, or with hydroxyl groups, linear or branched C 1 -C 6 alkoxyl groups, carboxyl groups, cyano groups, or with a 2,2,6,6-tetramethylpiperidine group; a linear or branched C 2 -C 6 alkenyl group; an aryl group selected from phenyl, biphenyl and naphthyl, said aryl group optionally substituted with linear or branched (C 1 -C 6 ) alkoxyl groups, carboxyl groups, amine groups, N,N-dialkyl (C 1 -C 6 ) amine groups; a benzyl group;
• R 1 and R 2 represent a linear or branched C 1 -C 10 alkyl group, said alkyl group optionally substituted with 1-10 halogen atoms selected from fluorine, chlorine and bromine, or with hydroxyl groups, linear or branched C 1 -C 6 alkoxyl groups, carboxyl groups, cyano groups; a linear or branched C 2 -C 10 alkenyl group; a benzyl group; a linear or branched C 1 -C 6 alkoxyl group; an N-alkyl (C 1 -C 6 ) amine group; an N,N-dialkyl (C 1 -C 6 ) amine group; or R 1 and R 2 , considered jointly with the carbon atom to which they are bound, represent a C 4 -C 10 cycloalkyl group, said cycloalkyl group optionally substituted with halogen atoms selected from fluorine, chlorine and bromine, or with hydroxy
• R 3 , R 4 , R 5 and R 6 the same or different, represent a hydrogen atom; a halogen atom selected from fluorine, chlorine, bromine and iodine; a linear or branched C 1 -C 6 alkyl group, said alkyl group optionally substituted with 1-6 halogen atoms selected from fluorine, chlorine and bromine, or with hydroxyl groups, linear or branched C 1 -C 6 alkoxyl groups, cyano groups; a benzyl group; a hydroxyl group; a linear or branched C 1 -C 6 alkoxyl group; an amine group; an N-alkyl (C 1 -C 6 ) amine group; an N,N-dialkyl (C 1 -C 6 ) amine group; a piperidine, piperazine or morpholine group; a C 1 -C 6 carboxyalkyl group; a C 2 -C 6 carboxyalkenyl group;
• R 7 represents a hydrogen atom; a halogen atom selected from fluorine, chlorine and bromine; a linear or branched C 1 -C 6 alkyl group; a linear or branched C 1 -C 6 alkoxyl group; a phenyl group; a phenoxyl group;
• P represents a monocyclic or polycyclic aromatic nucleus, belonging to one of the following types: benzenic represented by general formula (II); naphthalenic represented by general formula (III); quinolinic represented by general formula (IV); isoquinolinic represented by general formula (V); cumarinic represented by general formula (VI); quinazolinic represented by general formula (VII); phenanthrenic represented by general formula (VIII); anthracenic represented by general formula (IX):
• R 8 and R 13 , R 14 and R 21 , R 22 and R 28 , R 30 and R 35 , R 36 and R 41 , R 44 and R 47 , R 48 and R 57 , R 58 and R 67 represent the condensation points with the oxazine ring, the other substituents having the same meaning described under point c).
• Preferred compounds having general formula (I) for the purposes of the present invention are those in which:
• R represents one of the following groups: methyl, ethyl, isopropyl, 2-allyl, 2-hydroxyethyl, 2-carboxymethyl, phenyl, 4-N,N-dimethylaminoaniline, 4-methoxybenzene, 4-cyanobenzene;
• R 1 and R 2 represent a methyl or phenyl group; or considered jointly with the carbon atom to which they are bound, represent a cyclohexyl group;
• R 3 , R 4 , R 5 and R 6 represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or one of the following groups: methyl, isopropyl, hydroxyl, methoxyl, N,N-dimethylamine, piperidine, morpholine, carboxyl, carboxymethyl, N,N-dimethylcarboxyamide, cyano, nitro, methylketone, phenylketone, phenyl;
• R 7 represents a hydrogen atom, a chlorine atom, a bromine atom, a methyl group or a phenyl group
• P represents one of the groups having general formula (II) to (IX), wherein:
• R 8 and R 13 , R 14 and R 21 , R 22 and R 28 , R 30 and R 35 , R 36 and R 41 , R 44 and R 47 , R 48 and R 57 , R 58 and R 67 independently represent the condensation point with the oxazine ring and the other substituents each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, or one of the following groups: methyl, isopropyl, hydroxyl, methoxyl, 2-hydroxyethyl, 2-allyl, piperidine, morpholine, N,N-dimethylamine, carboxyl, carboxymethyl, N,N-dimethylcarboxyamide, cyano, nitro, methylketone, ethylketone, phenylketone, methylthiol;
• a further object of the present invention relates to a process for the preparation of the photochromatic compounds having general formula (I).
• the photochromatic compounds having general formula (I) can be prepared by the condensation of isoindoline compounds having general formula (X):
• reaction product is carried out in the presence of an inert organic solvent such as, for example, ethyl alcohol, isopropanol, toluene, or a mixture of these solvents, at a temperature ranging from 50° C. to 100° C., preferably between 60° C. and 75° C., for a time ranging from 1 hour to 10 hours, preferably between 2 hours and 5 hours.
• an inert organic solvent such as, for example, ethyl alcohol, isopropanol, toluene, or a mixture of these solvents
• reaction product is carried out in the presence of an inert organic solvent such as, for example, ethyl alcohol, isopropanol, toluene, or a mixture of these solvents, and in the presence of aqueous ammonia at 30%, at a temperature ranging from 50° C. to 100° C., preferably between 60° C. and 75° C., for a time ranging from 1 hour to 10 hours, preferably between 2 hours and 3 hours.
• the reaction product thus obtained is, generally, purified by elution on a silica column and subsequent crystallization from a solvent such as, for example, acetone, toluene, heptane.
• the isoindoline compounds having general formula (X) can be prepared according to procedures known in the art and described, for example, in: “Tetrahedron” (1966), Vol. 22, page 2481; “Journal of Organic Chemistry” (1979), Vol. 44, page 1519; “Angewandte Chemie International (1968), Vol. 7, page 373.
• the isoindoline compounds having general formula (X) are usually kept in the form of salts such as, for example, iodides, bromides, chlorides, as the tree base is easily oxidated by the air.
• nitrous compounds having general formula (XI) can be prepared by the reaction of phenol compounds with nitrous acid or butyl nitrite, as described, for example, in Italian patent 1.176.858.
• aromatic 1,2-quinones having general formula (XII) can be prepared as described, for example, in: “Journal of American Chemical Society” (1952), Vol. 74, page 278; Chemical Abstract 103-104923q; in European patent EP 245.020 and in U.S. Pat. No. 5,446,150.
• isoindoline compounds having general formula (X) are the following, represented by formula (Xa) corresponding to 1,1,2,4,7-pentamethyl-3-methylene-isoindoline and formula (Xb) corresponding to 1,1,4,7-tetramethyl-N-phenyl-3-methylene-isoindoline:
• nitrous compounds having general formula (XI) are the following, represented by formula (XIa) corresponding to 1-nitrous-2-naphthol, by formula (XIb) corresponding to 2-nitrous-1-naphthol, by formula (XIc) corresponding to 5-nitrous-6-hydroxy-quinoline, by formula (XId) corresponding to 1-nitrous-2-naphthol-6-propan(1)one and by formula (XIe) corresponding to 10-nitrous-9-phenanthrol:
• aromatic 1,2-quinone compounds having general formula (XII) are the following, represented by formula (XIIa) corresponding to 1,2-naphthoquinone-4-morpholine, formula (XIIb) corresponding to 1,2-naphthoquinone-4-piperidine and by formula (XIIc) corresponding to 1,2-naphthoquinone-4-(dimethylaniline):
• the photochromatic compounds having general formula (I) of the present invention are colourless or slightly yellowish crystalline products.
• the photochromatic compounds having general formula (I) can be applied to the surface or incorporated in mass into the desired articles, using techniques already known in the art and described hereunder.
• Some polymeric photochromatic end-articles can be obtained with moulding techniques such as, for example, injection or compression moulding, starting from polymers in which the photochromatic compound having formula (I) is homogeneously dispersed in mass.
• the photochromatic compound having general formula (I) can be dissolved in a solvent, together with the polymeric material such as, for example, polymethyl methacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate butyrate or epoxy, polysiloxane, urethane resin.
• a solvent such as, for example, polymethyl methacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate butyrate or epoxy, polysiloxane, urethane resin.
• the mixture thus obtained is deposited on a transparent carrier to form, after evaporation of the solvent, a photochromatic coating.
• the photochromatic compound having general formula (I) can also be added to a polymerizable monomer such as, for example, a meth(acrylic) or allyl carbonate monomer, so that, after polymerization carried out in the presence of a suitable initiator such as, for example, azo-bis(isobutyronitrile) in the case of the meth(acrylic) monomer or a peroxyketal in the case of the allyl carbonate monomer, they are uniformly incorporated in the resin formed.
• a suitable initiator such as, for example, azo-bis(isobutyronitrile) in the case of the meth(acrylic) monomer or a peroxyketal in the case of the allyl carbonate monomer
• the photochromatic compound having general formula (I) can be applied to a transparent substrate such as, for example, polycarbonate, polymethyl methacrylate or polydiethylene glycol bis(allyl carbonate), by surface impregnation obtained by putting the substrate in contact, at a suitable temperature, with a solution or dispersion containing the photochromatic compound having general formula (I), operating according to the method described, for example, in U.S. Pat. No. 5,130,353.
• a transparent substrate such as, for example, polycarbonate, polymethyl methacrylate or polydiethylene glycol bis(allyl carbonate
• the photochromatic compounds having general formula (I) of the present invention have the characteristic of being able to be incorporated in mass or using one of the techniques described above, into various organic polymers such as, for example, high density polyethylene, low density polyethylene, ethylene-vinylacetate copolymer, polyether amides, polypropylene, polymethylmethacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate butyrate, epoxy, polysiloxane or urethane resins, polycarbonate, polydiethylene glycol bis(allyl carbonate), polyamides, polyesters, polystyrene, vinyl polychloride, polymethylacrylate, polyethylacrylate, siliconic polymers.
• organic polymers such as, for example, high density polyethylene, low density polyethylene, ethylene-vinylacetate copolymer, polyether amides, polypropylene, polymethylmethacrylate, polyvinyl alcohol, polyvinyl butyral, cellulose acetate buty
• the photochromatic compounds having general formula (I) of the present invention can be optionally used in the presence of the usual additives for organic polymers such as, for example, phenol antioxidants, sterically hindered amines, benzotriazoles, phosphites or phosphonites.
• organic polymers such as, for example, phenol antioxidants, sterically hindered amines, benzotriazoles, phosphites or phosphonites.
• a further object of the present invention therefore relates to polymeric compositions comprising the above polymeric materials and the above photochromatic compounds having general formula (I), optionally in the presence of the above polymeric additives, and the photochromatic articles obtained from their processing.
• the photochromatic compounds having general formula (I) of the present invention have a photochromatic activity also at room temperature and, surprisingly, in some cases, their photochromatic activity is higher than that of products belonging to the group of spiro-indolino-oxazines.
• the photochromatic compounds having general formula (I) of the present invention can be used as such, mixed with each other, or combined with other suitable organic photochromatic compounds to obtain, after activation, the formation of different colourings such as, green, brown and grey.
• Photochromatic compounds belonging to the group of spiro-indolino-oxazines or spiro-pyranes described in the art such as, for example, in U.S. Pat. No. 5,066,818, are particularly useful for the purpose.
• the above mixture is heated to 80° C., under a nitrogen atmosphere, for 24 hours. At the end, the mixture is cooled and subsequently extracted with 30 ml of hexane.
• the aqueous phase obtained is treated with sodium hydroxide at 30% until pH 14 is reached: a yellow-white precipitate is thus formed which is rapidly filtered and washed with 30 ml of water and 10 ml of hexane.
• a quantity equal to 23.5 g of the above product is placed in a 100 ml inox steel autoclave together with 20 ml of toluene and 16 g of methyliodide.
• the autoclave is heated to 85° C. and is maintained at this temperature, under a nitrogen atmosphere, for 6 hours.
• the autoclave is cooled to room temperature and the raw product is filtered obtaining a crystalline precipitate which is washed with 20 ml of ethyl acetate and finally with 20 ml of hexane.
• the above mixture is heated to 80° C., under a nitrogen atmosphere, for 24 hours. At the end, the mixture is cooled and subsequently extracted with 30 ml of hexane.
• the aqueous phase obtained is treated with sodium hydroxide at 30% until a pH 14 is reached: a yellow-white precipitate is thus formed which is rapidly filtered and washed with 30 ml of water and 20 ml of hexane.
• a quantity equal to 25 g of the above product is placed in a 100 ml inox steel autoclave together with 20 ml of toluene and 18 g of methyliodide.
• the autoclave is heated to 85° C. and is maintained at this temperature, under a nitrogen atmosphere, for 6 hours.
• the autoclave is cooled to room temperature and the raw product is filtered obtaining a crystalline precipitate which is washed with 20 ml of ethyl acetate and finally with 20 ml of hexane.
• the raw photochromatic product thus obtained is then purified again by crystallization from toluene.
• the raw photochromatic product thus obtained is then purified again by crystallization from toluene.
• the dry residue obtained is dissolved in 20 ml of isopropanol to which 2 ml of triethylamine and 2.65 g of 5-nitrous-6-hydroxy-quinoline [Compound (XIc)] are added and the mixture is heated to 70° C., under a nitrogen atmosphere and under stirring, for 4.5 hours.
• the reaction raw product obtained is then purified by passage on a silica gel column eluating with a mixture of heptane/toluene in a ratio of 1/1.
• the raw photochromatic product thus obtained is then purified again by crystallization from toluene.
• the dry residue obtained is dissolved in 20 ml of isopropanol to which 2 ml of triethylamine and 3.4 g of 1-nitrous-2-naphthol-6-propan(1)one [Compound (XId)] are added: the mixture is heated to 70° C. and maintained at this temperature, under stirring, under a nitrogen atmosphere, for three hours.
• the reaction raw product obtained is then purified by passage on a silica gel column eluating with a mixture of heptane/toluene in a ratio of 1/1.
• the raw photochromatic product thus obtained is then purified again by crystallization from toluene.
• the raw photochromatic product thus obtained is then purified again by crystallization from toluene.
• the raw photochromatic product thus obtained is then purified again by crystallization from toluene.
• the photochromatic activity is evaluated in methanol and toluene, at 20° C., of Compounds (Ia)-(If) obtained as described above in Examples 3-8.
• Solutions are prepared at a concentration equal to about 10 ⁇ 4 M (the exact concentrations are indicated in Table 9) of the various Compounds (Ia)-(If) in the two solvents and subsequently 1.3 ml of each solution is placed, individually, in a 1 cm quartz cell having a square base inlet.
• the quartz cell containing the solution is introduced into a Peltier temperature control system (HP accessory—HP 89090A), with the possibility of magnetic stirring during the measuring, and is irradiated from above with a Philips UVA lamp with an irradiance equal to 9 Watt/cm 2 supported on the cell itself.
• the irradiance time varies from sample to sample (60′′-180′′) to guarantee the maximum degree of colouring of the solution.

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• Chemical & Material Sciences (AREA)
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• Materials Engineering (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
• Nitrogen Condensed Heterocyclic Rings (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Plural Heterocyclic Compounds (AREA)
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Citations (4)

• 1997
  • 1997-07-03 IT IT97MI001573A patent/IT1292461B1/it active IP Right Grant
• 1998
  • 1998-07-01 EP EP98939568A patent/EP0994879B1/en not_active Expired - Lifetime
  • 1998-07-01 JP JP50632199A patent/JP2002507980A/ja not_active Ceased
  • 1998-07-01 US US09/446,904 patent/US6414057B1/en not_active Expired - Fee Related
  • 1998-07-01 WO PCT/EP1998/003994 patent/WO1999001457A1/en active IP Right Grant
  • 1998-07-01 AT AT98939568T patent/ATE250613T1/de not_active IP Right Cessation
  • 1998-07-01 KR KR1019997012438A patent/KR100569654B1/ko not_active Expired - Fee Related
  • 1998-07-01 DE DE69818471T patent/DE69818471T2/de not_active Expired - Fee Related
  • 1998-07-01 AU AU88033/98A patent/AU8803398A/en not_active Abandoned
  • 1998-07-03 AR ARP980103237A patent/AR010923A1/es unknown
  • 1998-07-03 ZA ZA985807A patent/ZA985807B/xx unknown

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